EP0512371A2 - Granular phosphate-free agents for automatic dishwashing - Google Patents
Granular phosphate-free agents for automatic dishwashing Download PDFInfo
- Publication number
- EP0512371A2 EP0512371A2 EP92107235A EP92107235A EP0512371A2 EP 0512371 A2 EP0512371 A2 EP 0512371A2 EP 92107235 A EP92107235 A EP 92107235A EP 92107235 A EP92107235 A EP 92107235A EP 0512371 A2 EP0512371 A2 EP 0512371A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- acid
- alkali
- detergent according
- dishwashing detergent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004851 dishwashing Methods 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007844 bleaching agent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 102000004190 Enzymes Human genes 0.000 claims abstract description 9
- 108090000790 Enzymes Proteins 0.000 claims abstract description 9
- 229940088598 enzyme Drugs 0.000 claims abstract description 9
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012190 activator Substances 0.000 claims abstract description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 5
- 239000011976 maleic acid Substances 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 102000013142 Amylases Human genes 0.000 claims abstract description 4
- 108010065511 Amylases Proteins 0.000 claims abstract description 4
- 102000004882 Lipase Human genes 0.000 claims abstract description 4
- 108090001060 Lipase Proteins 0.000 claims abstract description 4
- 239000004367 Lipase Substances 0.000 claims abstract description 4
- 102000035195 Peptidases Human genes 0.000 claims abstract description 4
- 108091005804 Peptidases Proteins 0.000 claims abstract description 4
- 239000004365 Protease Substances 0.000 claims abstract description 4
- 150000007513 acids Chemical class 0.000 claims abstract description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 4
- 235000019418 amylase Nutrition 0.000 claims abstract description 4
- 229940025131 amylases Drugs 0.000 claims abstract description 4
- 235000019421 lipase Nutrition 0.000 claims abstract description 4
- UOQHWNPVNXSDDO-UHFFFAOYSA-N 3-bromoimidazo[1,2-a]pyridine-6-carbonitrile Chemical compound C1=CC(C#N)=CN2C(Br)=CN=C21 UOQHWNPVNXSDDO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 102000004157 Hydrolases Human genes 0.000 claims abstract description 3
- 108090000604 Hydrolases Proteins 0.000 claims abstract description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 3
- 229920001519 homopolymer Polymers 0.000 claims abstract description 3
- 229940099563 lactobionic acid Drugs 0.000 claims abstract description 3
- 239000002736 nonionic surfactant Substances 0.000 claims abstract 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract 3
- 239000002270 dispersing agent Substances 0.000 claims abstract 2
- 150000002170 ethers Chemical class 0.000 claims abstract 2
- 150000007524 organic acids Chemical class 0.000 claims abstract 2
- 235000005985 organic acids Nutrition 0.000 claims abstract 2
- 150000004965 peroxy acids Chemical class 0.000 claims abstract 2
- 235000000346 sugar Nutrition 0.000 claims abstract 2
- 150000008163 sugars Chemical class 0.000 claims abstract 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract 2
- 239000003599 detergent Substances 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 238000005187 foaming Methods 0.000 claims description 7
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000176 sodium gluconate Substances 0.000 claims description 6
- 235000012207 sodium gluconate Nutrition 0.000 claims description 6
- 229940005574 sodium gluconate Drugs 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 claims description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920001184 polypeptide Polymers 0.000 claims description 2
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 2
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 239000003760 tallow Substances 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims 4
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical group CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 claims 4
- 150000001447 alkali salts Chemical class 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 229940071207 sesquicarbonate Drugs 0.000 claims 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 7
- 239000010452 phosphate Substances 0.000 abstract description 7
- -1 alkali metal gluconate Chemical class 0.000 abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 5
- 229940050410 gluconate Drugs 0.000 abstract description 4
- 239000006260 foam Substances 0.000 abstract description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 abstract 1
- 150000008041 alkali metal carbonates Chemical class 0.000 abstract 1
- 230000004151 fermentation Effects 0.000 abstract 1
- 238000000855 fermentation Methods 0.000 abstract 1
- 239000003352 sequestering agent Substances 0.000 abstract 1
- 238000009472 formulation Methods 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000009918 complex formation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 150000002597 lactoses Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/221—Mono, di- or trisaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
Definitions
- the invention relates to a granular phosphate-free agent for automatic dishwashing.
- Conventional dishwashing detergents for the dishwasher essentially consist of the components alkali tripolyphosphate, alkali metasilicate and alkali carbonate.
- organic additives such as non-foaming surfactants, polycarboxylates (homopolymers of acrylic acid or copolymers with maleic acid) chlorine releasers (e.g. sodium dichloroisocyanurate) are used.
- DE-AS 21 49 251, DE-OS 21 62 673 and DE-OS 24 35 479 already describe phosphate-free compositions for automatic dishwashing, which include as important components polycarboxylates and polycarboxylic acids, e.g. Citric acid or tartaric acid, and some are phosphate-free.
- dishwashing detergents which have recently been on the German market, are based on trisodium citrate combined with polycarboxylates as the most important phosphate substitute.
- citrate became possible because its calcium binding power is much better in combination with sodium disilicate than with the more alkaline sodium metasilicate.
- these dishwashing detergents contain nonionic non-foaming surfactants, polycarboxylates, enzymes, oxygen-based bleaches (for example sodium perborate) and bleach activators such as TAED.
- complexing agents such as e.g. NTA or EDTA, recommended as a hardness binder.
- the present test material shows that formulations containing these substances actually show excellent properties in the removal of tea.
- the destruction of the tea dye complex with calcium ions is particularly important here.
- the use of these compounds is ecologically questionable, since there is a risk of remobilization of heavy metals from the sediments of surface waters.
- the use of larger amounts of phosphonates as complexing agents is also not advisable from an ecological point of view.
- the present invention has for its object to provide a granular, phosphate-free dishwashing detergent for the dishwasher, the phosphate substitutes of which contribute as little as possible to water pollution.
- the flushing performance according to DIN 44 990 should at least correspond to the IEC standard cleaner with reduced risk potential for the consumer.
- sodium gluconate in a highly alkaline medium is known.
- highly alkaline industrial cleaners e.g. used in bottle washing
- polyphosphates are subject to strong hydrolysis, especially at elevated temperatures; at the same time, the complex formation constant with calcium ions drops drastically, so that the effects of phosphates are severely impaired.
- the sodium gluconate shows very strong advantages because it is not hydrolyzed and its complex formation constant with calcium ions increases with increasing pH. At pH values below 12.5, the stability of the complex decreases, and below this, calcium salts precipitate in the temperature range of 65 ° C of interest.
- an alkali metal gluconate in particular sodium gluconate
- lactose derivatives such as the salts of lactobionic acid.
- the combination according to the invention of a polycarboxylate (polyacrylate or copolymers with maleic acid), preferably copolymers with sodium disilicate (ratio SiO2: Na2O is 1.7: 1 to 2.3: 1) and sodium gluconate shows a superior effect compared to formulations based on citrate.
- the use of layered silicates known from DE-OS 36 27 773 is also possible since, apart from the lack of water of crystallization, they have a stoichiometry corresponding to the amorphous disilicate.
- Biodegradable polypeptides that are obtained from natural sources are also used as the polymeric sequester.
- Such products derived from fishing waste, e.g. extracted from mussels are available under the trademark Cygnus from Cygnus Corporation, Illinois (USA).
- sodium citrate like the complexing agent NTA already mentioned, forms a 1: 1 adduct with the calcium ions, equimolar amounts are necessary to bind the water hardness. Therefore, sodium citrate is mostly used in higher percentages. Formulations up to more than 40% by weight of citrate are not uncommon. The biodegradation of citrate in the wastewater treatment plant is extremely fast, but the biological oxygen demand is high, especially with the necessary high levels in the cleaners.
- the dishwasher detergent according to the invention for the dishwasher manages with a fraction of sodium gluconate compared to citrate. With comparable degradability of the gluconate, which also occurs naturally, there is a significantly reduced oxygen requirement due to the lower amount used, since the wastewater pollution with organic substances is greatly reduced. The total proportion of organic substances, apart from the enzymes, is only slightly more than 14% by weight in the formulation according to the invention.
- the inorganic substances sodium disilicate and sodium carbonate used can be regarded as ecologically harmless.
- the cleaning effect can be very specifically improved in the combination of soda / disilicate / polycarboxylate / gluconate according to the invention with enzymes.
- enzymes preferably amylases and proteases, but also lipases, with very good activity are to be used in the composition according to the invention.
- the bleaching agent in the present cleaner consists of an active oxygen compound.
- an active oxygen compound e.g. Peroxo compounds or peroxohydrates, e.g. Alkali perborate, alkali carbonate, peroxohydrate, alkali peroxosulfate, hydrogen peroxide, urea, preferably sodium perborate monohydrate.
- an activator e.g. from the group of compounds, which split off peracetic acid under the action of hydrogen peroxide.
- the TAED is particularly worth mentioning here.
- Non-foaming or low-foaming surfactants are particularly advantageous in dishwashers because they suppress the foam generated by the spray arm.
- the biodegradable surfactants of the fatty alcohol type with EO / PO chains have proven successful here.
- biodegradable anionic surfactants which are derived from glycine have also proven to be advantageous in the agent according to the invention.
- These polycarboxyglycinates of the general formula R- (N- (CH2) 3-CH2COONa) n-CH2COONa also contribute to the sequestration of water hardness due to their nitrogen atoms.
- R stands for a fatty alkyl residue, such as tallow fat.
- Preferred recipes are the subject of the dependent claims.
- the rate of dissolution in water can be delayed, as is the case with crystalline layered silicate.
- granular amorphous sodium disilicate shows positive behavior.
- Additives customary for such cleaners such as e.g. Fragrances and dyes, defoamers, pouring aids, extenders and extenders are added. However, they do not contribute to the cleaning effect, but can influence consumer acceptance or improve the storage stability of the formulation.
- Buffer substances can also be added to regulate the pH.
- the inorganic hydrogen carbonates or sesquicarbonates are particularly worth mentioning here.
- organic compounds e.g. Alkaline acetates, which make little contribution to cleaning performance, can serve this purpose.
- These buffers can set the pH to a lower level so that the agent no longer has to be classified as an irritant or meets even the strictest legal requirements.
- Example 1 is a known agent, while Examples 2-8 relate to compositions according to the invention.
- composition according to the invention when used with the same dosage of 25 g, a much better washing result is achieved than with the IEC standard cleaner.
- very stubborn, starchy dirt, such as oatmeal is removed very well.
- spinach which can only be removed by sufficient dispersing and emulsifying effects of the cleaner, is removed very well.
- the environmental impact is reduced by a much lower dosage in the dishwasher.
- the amount used can be reduced by up to 50% compared to conventional cleaners.
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Abstract
Description
Die Erfindung betrifft ein granuläres phosphatfreies Mittel für das maschinelle Geschirrspülen.The invention relates to a granular phosphate-free agent for automatic dishwashing.
Konventionelle Geschirrspülmittel für die Geschirrspülmaschine bestehen im wesentlichen aus den Komponenten Alkalitripolyphosphat, Alkalimetasilikat und Alkalicarbonat. Daneben sind organische Additive wie nichtschäumende Tenside, Polycarboxylate (Homopolymere der Acrylsäure oder Copolymere mit Maleinsäure) Chlorabspalter (z.B. Natriumdichlorisocyanurat) im Einsatz.Conventional dishwashing detergents for the dishwasher essentially consist of the components alkali tripolyphosphate, alkali metasilicate and alkali carbonate. In addition, organic additives such as non-foaming surfactants, polycarboxylates (homopolymers of acrylic acid or copolymers with maleic acid) chlorine releasers (e.g. sodium dichloroisocyanurate) are used.
Neuere Entwicklungen zielen auf den Ersatz von Phosphat, um die Eutrophierung der Oberflächengewässer zu reduzieren.Recent developments aim to replace phosphate in order to reduce the eutrophication of surface waters.
Neben dieser ökologischen Seite ist auch die Toxikologie von Bedeutung. Gesetzliche Massnahmen führen dazu, dass hochalkalische Produkte ab Mitte 1991 in Deutschland nur noch in kindergesicherten Verpackungen auf den Markt gebracht werden dürfen. In anderen Ländern wurde dieses Gesetz schon vor einiger Zeit erlassen. Dies führte zur Entwicklung von Geschirr-Reinigern mit verminderter Alkalität, um die Gefährdung des Verbrauchers, vor allem von Kindern, zu verringern, ohne andererseits das Müllproblem durch die aufwendigere Verpackung zu vergrössern. Gleichzeitig verzichten die neuen Reiniger auf Chlorverbindungen.In addition to this ecological side, toxicology is also important. Legal measures mean that from mid-1991, highly alkaline products in Germany may only be brought onto the market in child-resistant packaging. In other countries, this law was passed some time ago. This led to the development of dishwashing detergents with reduced alkalinity in order to reduce the risk to consumers, especially children, without, on the other hand, increasing the waste problem due to the more complex packaging. At the same time, the new cleaners do without chlorine compounds.
Bereits in DE-AS 21 49 251, DE-OS 21 62 673 und DE-OS 24 35 479 sind phosphatfreie Zusammensetzungen zum maschinellen Geschirrspülen beschrieben, die u.a. als wichtige Bestandteile Polycarboxylate und Polycarbonsäuren, wie z.B. Citronensäure oder Weinsäure, enthalten und teilweise phosphatfrei sind.DE-AS 21 49 251, DE-OS 21 62 673 and DE-OS 24 35 479 already describe phosphate-free compositions for automatic dishwashing, which include as important components polycarboxylates and polycarboxylic acids, e.g. Citric acid or tartaric acid, and some are phosphate-free.
Die Geschirrspülmittel der neuen Generation, die sich seit kurzem auf dem deutschen Markt befinden, basieren auf Trinatriumcitrat kombiniert mit Polycarboxylaten als wichtigstem Phosphataustauschstoff. Der Einsatz des Citrates wurde möglich, da seine Calcium-Bindekraft in Kombination mit Natriumdisilikat wesentlich besser ist, als mit dem höher alkalischen Natriummetasilikat. Daneben enthalten diese Geschirrspülmittel nichtionische nichtschäumende Tenside, Polycarboxylate, Enzyme, Bleichmittel auf Sauerstoffbasis (z.B. Natriumperborat) und Bleichaktivatoren, wie z.B. TAED.The new generation of dishwashing detergents, which have recently been on the German market, are based on trisodium citrate combined with polycarboxylates as the most important phosphate substitute. The use of citrate became possible because its calcium binding power is much better in combination with sodium disilicate than with the more alkaline sodium metasilicate. In addition, these dishwashing detergents contain nonionic non-foaming surfactants, polycarboxylates, enzymes, oxygen-based bleaches (for example sodium perborate) and bleach activators such as TAED.
Als umweltfreundliche Alternativen werden auch solche Mittel empfohlen, die Zeolith A als Ersatz für das Phosphat enthalten. Diese unlöslichen Stoffe können allerdings zur Bildung von weissen Belägen führen. Ausserdem kann auch das Problem von beim Kochvorgang auf dem Geschirr aus kristallisiertem Calciumcarbonat nicht gelöst werden, da der unlösliche Zeolith A als Ionenaustauscher wirkt und nur die gelöste Wasserhärte binden kann. Ausgefallenes Calciumcarbonat kann er nicht ausreichend wieder in Lösung bringen.Agents that contain zeolite A as a replacement for the phosphate are also recommended as environmentally friendly alternatives. However, these insoluble substances can lead to the formation of white deposits. In addition, the problem of cooking on the dishes made of crystallized calcium carbonate cannot be solved, since the insoluble zeolite A acts as an ion exchanger and can only bind the dissolved water hardness. Precipitated calcium carbonate cannot be brought back into solution sufficiently.
Weiterhin werden teilweise in den obengenannten und anderen Schriften Komplexbildner, wie z.B. NTA oder EDTA, als Härtebinder empfohlen. Das vorliegende Untersuchungsmaterial zeigt, dass Formulierungen, die diese Stoffe enthalten, tatsächlich hervorragende Eigenschaften bei der Entfernung von Tee zeigen. Hier kommt es besonders auf die Zerstörung des Komplexes des Tee-Farbstoffes mit Calciumionen an. Der Einsatz dieser Verbindungen ist aber ökologisch bedenklich, da eine Remobilisierung von Schwermetallen aus den Sedimenten der Oberflächengewässer zu befürchten ist. Auch der Einsatz von grösseren Mengen Phosphonaten als Komplexbildner ist unter dem ökologischen Gesichtspunkt nicht ratsam.Furthermore, complexing agents such as e.g. NTA or EDTA, recommended as a hardness binder. The present test material shows that formulations containing these substances actually show excellent properties in the removal of tea. The destruction of the tea dye complex with calcium ions is particularly important here. However, the use of these compounds is ecologically questionable, since there is a risk of remobilization of heavy metals from the sediments of surface waters. The use of larger amounts of phosphonates as complexing agents is also not advisable from an ecological point of view.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein granuläres phosphatfreies Geschirrspülmittel für die Spülmaschine zu schaffen, dessen Phosphatersatzstoffe möglichst wenig zur Gewässerbelastung beitragen. Ausserdem soll bei verringertem Gefahrenpotential für den Verbraucher die Spülleistung nach DIN 44 990 mindestens dem IEC-Standardreiniger entsprechen.The present invention has for its object to provide a granular, phosphate-free dishwashing detergent for the dishwasher, the phosphate substitutes of which contribute as little as possible to water pollution. In addition, the flushing performance according to DIN 44 990 should at least correspond to the IEC standard cleaner with reduced risk potential for the consumer.
Diese Aufgabe wird erfindungsgemäss durch die kennzeichnenden Merkmale des Anspruches 1 gelöst. Durch den geringen Anteil an organischen Verbindungen ist die Belastung der Gewässer durch das erfindungsgemässe Spülmittel äusserst gering.According to the invention, this object is achieved by the characterizing features of claim 1. Due to the low proportion of organic compounds, the pollution of the water by the detergent according to the invention is extremely low.
Bekannt ist der Einsatz von Natriumgluconat in hochalkalischem Medium. In hochalkalischen Industriereinigern, wie sie z.B. in der Flaschenwäsche zum Einsatz kommen, unterliegen Polyphosphate besonders bei erhöhter Temperatur starker Hydrolyse; gleichzeitig sinkt die Komplexbildungskonstante mit Calciumionen drastisch ab, so dass Phosphate stark in ihrer Wirkung beeinträchtigt werden. Hier zeigt das Natriumgluconat sehr starke Vorteile, da es nicht hydrolysiert wird, und seine Komplexbildungskonstante mit Calciumionen mit steigendem pH-Wert zunimmt. Bei pH-Werten unterhalb von 12,5 wird die Stabilität des Komplexes geringer, und darunter kommt es im interessierenden Temperaturbereich von 65° C zur Ausfällung von Calciumsalzen.The use of sodium gluconate in a highly alkaline medium is known. In highly alkaline industrial cleaners, e.g. used in bottle washing, polyphosphates are subject to strong hydrolysis, especially at elevated temperatures; at the same time, the complex formation constant with calcium ions drops drastically, so that the effects of phosphates are severely impaired. Here the sodium gluconate shows very strong advantages because it is not hydrolyzed and its complex formation constant with calcium ions increases with increasing pH. At pH values below 12.5, the stability of the complex decreases, and below this, calcium salts precipitate in the temperature range of 65 ° C of interest.
Überraschenderweise kann ein Alkaligluconat, insbesondere Natriumgluconat, in den Zusammensetzungen der vorliegenden Erfindung trotz niedrigem pH-Wert (9,5 - 11) bereits in geringer Dosierung eine entscheidende Rolle als Phosphatersatzstoff übernehmen. Ähnliche Effekte sind auch mit Lactoseabkömmlingen, wie der Salze der Lactobionsäure, zu erzielen. Die erfindungsgemässe Kombination eines Polycarboxylates (Polyacrylat oder Copolymere mit Maleinsäure), vorzugsweise Copolymeren mit Natriumdisilikat (Verhältnis SiO₂:Na₂O beträgt 1,7:1 bis 2,3:1) und Natriumgluconat, zeigt eine überlegene Wirkung gegenüber Formulierungen auf Basis Citrat. Ebenso ist auch die aus DE-OS 36 27 773 bekannte Verwendung von Schichtsilikaten möglich, da sie bis auf das fehlende Kristallwasser eine dem amorphen Disilikat entsprechende Stöchiometrie aufweisen.Surprisingly, an alkali metal gluconate, in particular sodium gluconate, can play a decisive role as a phosphate substitute in the compositions of the present invention, despite the low pH (9.5-11), even in low doses. Similar effects can also be achieved with lactose derivatives, such as the salts of lactobionic acid. The combination according to the invention of a polycarboxylate (polyacrylate or copolymers with maleic acid), preferably copolymers with sodium disilicate (ratio SiO₂: Na₂O is 1.7: 1 to 2.3: 1) and sodium gluconate, shows a superior effect compared to formulations based on citrate. Likewise, the use of layered silicates known from DE-OS 36 27 773 is also possible since, apart from the lack of water of crystallization, they have a stoichiometry corresponding to the amorphous disilicate.
Besonders überraschend ist, dass ein Zusatz von Natriumcarbonat die Reinigungsleistung nochmals wesentlich verbessert. Zur Stabilisierung der Aktivsauerstoff-Verbindung kann ein geringer Anteil an Phosphonat, wie z.B. HEDP, zum Einsatz kommen. In allen Natriumverbindungen kann das Natrium selbstverständlich auch durch andere Alkalimetalle ersetzt werden. Dies ist allerdings eine ökonomische Frage.It is particularly surprising that the addition of sodium carbonate significantly improves the cleaning performance. To stabilize the active oxygen compound, a small proportion of phosphonate, e.g. HEDP. In all sodium compounds, the sodium can of course also be replaced by other alkali metals. However, this is an economic question.
Als polymere Sequester kommen auch biologisch abbaubare Polypeptide zum Einsatz, die aus natürlichen Quellen gewonnen werden. Solche Produkte, die aus Abfällen der Fischerei, z.B. aus Muscheln, extrahiert werden, sind unter der Marke Cygnus der Cygnus Corporation, Illinois (USA), erhältlich.Biodegradable polypeptides that are obtained from natural sources are also used as the polymeric sequester. Such products derived from fishing waste, e.g. extracted from mussels are available under the trademark Cygnus from Cygnus Corporation, Illinois (USA).
Neben der sehr guten Reinigungsleistung über das ganze Spektrum der in DIN 44 990 genannten Anschmutzungen der erfindungsgemässen Zusammensetzung ist auch die sehr gute Inhibierung von Belagsbildung hervorzuheben. Eine schwankende Wasserqualität und ein nicht immer voll arbeitender Wasserenthärter (Ionenaustauscher) in der Spülmaschine können insbesondere bei Reiniger-Formulierungen, die grössere Mengen Alkalisilikate enthalten, zu ausgeprägten Ablagerungen von kristallinem Erdalkalisilikat, wie Calcium- und Magnesiumsilikat, führen. Diese weissen bis grauen Beläge fallen besonders auf der Innenseite der Spülmaschine, auf Gläsern und auf Edelstahlteilen, wie Besteck, unangenehm auf. Bevorzugt treten solche Ablagerungen bei phosphatfreien Formulierungen auf, wenn das Calcium bzw. Magnesium nicht genügend sequestriert wird. Das erfindungsgemässe maschinelle Geschirrspülmittel zeigt überraschenderweise sehr gute Belagsverhinderung, obwohl es weder harte Komplexbildner, wie z.B. NTA oder EDTA, noch weichere Komplexbildner, wie z.B. Zitronensäure, enthält.In addition to the very good cleaning performance across the entire spectrum of the soiling of the composition according to the invention specified in DIN 44 990, the very good inhibition of deposit formation should also be emphasized. Fluctuating water quality and a water softener (ion exchanger) that is not always fully functional in the dishwasher can lead to pronounced deposits of crystalline alkaline earth metal silicate, such as calcium and magnesium silicate, especially in cleaner formulations that contain large amounts of alkali silicates. These white to gray deposits are particularly unpleasant on the inside of the dishwasher, on glasses and on stainless steel parts such as cutlery. Such deposits preferably occur in phosphate-free formulations if the calcium or magnesium is not sequestered sufficiently. The machine dishwashing detergent according to the invention surprisingly shows very good deposit prevention, although it contains neither hard complexing agents, such as NTA or EDTA, nor softer complexing agents, such as citric acid.
Da Natriumcitrat, wie der bereits genannte Komplexbildner NTA, ein 1:1 Addukt mit den Calciumionen bildet, sind äquimolare Mengen zur Bindung der Wasserhärte nötig. Daher kommt Natriumcitrat meist in höheren Prozentanteilen zum Einsatz. Formulierungen bis über 40 Gew.% Citrat sind keine Seltenheit. Der biologische Abbau von Citrat in der Kläranlage geht zwar ausserordentlich schnell zu 100 % vonstatten, allerdings ist der biologische Sauerstoffbedarf hoch, insbesondere bei den notwendigerweise hohen Anteilen in den Reinigern. Demgegenüber kommt das erfindungsgemässe Geschirrspülmittel für die Spülmaschine mit einem Bruchteil an Natriumgluconat, verglichen mit Citrat, aus. Bei vergleichbarer Abbaubarkeit des ebenfalls in der Natur vorkommenden Gluconates ergibt sich durch die geringere Einsatzmenge ein erheblich reduzierter Sauerstoffbedarf, da die Abwasserbelastung mit organischen Stoffen stark reduziert ist. Der gesamte Anteil an organischen Stoffen, ausser den Enzymen, beträgt bei der erfindungsgemässen Rezeptur nur etwas mehr als 14 Gew.%. Die zum Einsatz gelangenden anorganischen Stoffe Natriumdisilikat und Natriumcarbonat können als ökologisch unbedenklich betrachtet werden.Since sodium citrate, like the complexing agent NTA already mentioned, forms a 1: 1 adduct with the calcium ions, equimolar amounts are necessary to bind the water hardness. Therefore, sodium citrate is mostly used in higher percentages. Formulations up to more than 40% by weight of citrate are not uncommon. The biodegradation of citrate in the wastewater treatment plant is extremely fast, but the biological oxygen demand is high, especially with the necessary high levels in the cleaners. In contrast, the dishwasher detergent according to the invention for the dishwasher manages with a fraction of sodium gluconate compared to citrate. With comparable degradability of the gluconate, which also occurs naturally, there is a significantly reduced oxygen requirement due to the lower amount used, since the wastewater pollution with organic substances is greatly reduced. The total proportion of organic substances, apart from the enzymes, is only slightly more than 14% by weight in the formulation according to the invention. The inorganic substances sodium disilicate and sodium carbonate used can be regarded as ecologically harmless.
Die Reinigungswirkung kann in der erfindungsgemässen Kombination Soda/Disilikat/Polycarboxylat/Gluconat mit Enzymen sehr spezifisch verbessert werden. Insbesondere sind in der erfindungsgemässen Zusammensetzung Hydrolasen, vorzugsweise Amylasen und Proteasen, aber auch Lipasen, mit sehr guter Wirkung einzusetzen.The cleaning effect can be very specifically improved in the combination of soda / disilicate / polycarboxylate / gluconate according to the invention with enzymes. In particular, hydrolases, preferably amylases and proteases, but also lipases, with very good activity are to be used in the composition according to the invention.
Da Enzyme von aktivem Chlor in der Spülflotte sehr schnell abgebaut und dadurch unwirksam werden, besteht in dem vorliegenden Reiniger das Bleichmittel aus einer Aktivsauerstoff-Verbindung. Hier können z.B. Peroxoverbindungen oder Peroxohydrate, wie z.B. Alkaliperborat, Alkalicarbonat, Peroxohydrat, Alkaliperoxosulfat, Wasserstoffperoxid, Harnstoff, vorzugsweise Natriumperborat-Monohydrat, zum Einsatz gelangen. Da Haushaltsspülmaschinen derzeit im Bereich von 40 - 65° C arbeiten, kann die Sauerstoffbleiche durch einen Aktivator, z.B. aus der Gruppe der Verbindungen, verbessert werden, die unter Einwirkung von Wasserstoffperoxid Peressigsäure abspalten. Insbesondere sei hier das TAED genannt.Since enzymes from active chlorine in the washing liquor are broken down very quickly and are therefore ineffective, the bleaching agent in the present cleaner consists of an active oxygen compound. Here e.g. Peroxo compounds or peroxohydrates, e.g. Alkali perborate, alkali carbonate, peroxohydrate, alkali peroxosulfate, hydrogen peroxide, urea, preferably sodium perborate monohydrate, are used. Since household dishwashers currently work in the range of 40 - 65 ° C, oxygen bleaching can be carried out by an activator, e.g. from the group of compounds, which split off peracetic acid under the action of hydrogen peroxide. The TAED is particularly worth mentioning here.
Tenside erniedrigen bekanntlich die Oberflächenspannung und tragen zur besseren Benetzung bei. In Geschirrspülmaschinen sind vor allem nicht- bzw. schwachschäumende Tenside sehr vorteilhaft, da sie den Schaum, der durch den Sprüharm erzeugt wird, unterdrücken. Bewährt haben sich hier die biologisch abbaubaren Tenside des Typs Fettalkohole mit EO/PO-Ketten.It is known that surfactants lower the surface tension and contribute to better wetting. Non-foaming or low-foaming surfactants are particularly advantageous in dishwashers because they suppress the foam generated by the spray arm. The biodegradable surfactants of the fatty alcohol type with EO / PO chains have proven successful here.
Als vorteilhaft haben sich in dem erfindungsgemässen Mittel aber auch ebenfalls sehr gut biologisch abbaubare anionische Tenside erwiesen, die sich von Glycin ableiten. Diese Polycarboxyglycinate der allgemeinen Formel R-(N-(CH2)3-CH2COONa)n-CH2COONa tragen durch ihre Stickstoffatome zusätzlich zur Sequestrierung der Wasserhärte bei. R steht hier für einen Fettalkyl-Rest, wie z.B. Talgfett.However, biodegradable anionic surfactants which are derived from glycine have also proven to be advantageous in the agent according to the invention. These polycarboxyglycinates of the general formula R- (N- (CH2) 3-CH2COONa) n-CH2COONa also contribute to the sequestration of water hardness due to their nitrogen atoms. R here stands for a fatty alkyl residue, such as tallow fat.
Bevorzugte Rezepturen sind Gegenstand der Unteransprüche. Zum Anspruch 2 ist anzumerken, dass die Lösegeschwindigkeit in Wasser verzögert werden kann, wie dies bei kristallinem Schichtsilikat der Fall ist. Insbesondere zeigt granuläres amorphes Natriumdisilikat ein positives Verhalten.Preferred recipes are the subject of the dependent claims. Regarding claim 2, it should be noted that the rate of dissolution in water can be delayed, as is the case with crystalline layered silicate. In particular, granular amorphous sodium disilicate shows positive behavior.
Dem erfindungsgemässen Mittel können ohne Probleme auch für solche Reiniger übliche Zusatzstoffe, wie z.B. Duft- und Farbstoffe, Entschäumer, Rieselhilfen, Stell- und Streckmittel, zugesetzt werden. Sie tragen allerdings nicht zur Reinigungswirkung bei, können aber die Akzeptanz beim Verbraucher beeinflussen oder die Lagerfähigkeit der Formulierung verbessern.Additives customary for such cleaners, such as e.g. Fragrances and dyes, defoamers, pouring aids, extenders and extenders are added. However, they do not contribute to the cleaning effect, but can influence consumer acceptance or improve the storage stability of the formulation.
Zur Regulierung des pH-Wertes sind auch Zusätze von Puffersubstanzen möglich. Hier sind vor allem die anorganischen Hydrogencarbonate oder Sesquicarbonate zu nennen. Aber auch organische Verbindungen, wie z.B. Alkaliacetate, die zur Reinigungsleistung kaum einen Beitrag leisten, können diesem Zweck dienen. Diese Puffer können den pH-Wert auf ein niedrigeres Niveau einstellen, so dass das Mittel nicht mehr als reizend eingestuft werden muss oder selbst strengste gesetzliche Vorgaben erfüllt.Buffer substances can also be added to regulate the pH. The inorganic hydrogen carbonates or sesquicarbonates are particularly worth mentioning here. But also organic compounds, e.g. Alkaline acetates, which make little contribution to cleaning performance, can serve this purpose. These buffers can set the pH to a lower level so that the agent no longer has to be classified as an irritant or meets even the strictest legal requirements.
Nachfolgend sind Beispiele der erfindungsgemässen Rezepturen in einer Tabelle wiedergegeben, wobei unter IEC ein Standardreiniger angegeben ist. Die Zusammensetzungen sind in Gew.% angegeben. Beim Beispiel 1 handelt es sich um ein bekanntes Mittel, während die Beispiele 2 - 8 erfindungsgemässe Zusammensetzungen betreffen.
Wie die angeführten Beispiele zeigen, wird beim Einsatz der erfindungsgemässen Zusammensetzung bei gleicher Dosierung von 25 g ein wesentlich besseres Spülergebnis erzielt als mit dem IEC-Standardreiniger. Insbesondere werden sehr hartnäckige stärkehaltige Verschmutzungen, wie Haferschleim, sehr gut entfernt. Aber auch der nur durch ausreichende dispergierende und emulgierende Wirkung des Reinigers entfernbare Spinat wird sehr gut entfernt.As the examples given show, when the composition according to the invention is used with the same dosage of 25 g, a much better washing result is achieved than with the IEC standard cleaner. In particular, very stubborn, starchy dirt, such as oatmeal, is removed very well. But also the spinach, which can only be removed by sufficient dispersing and emulsifying effects of the cleaner, is removed very well.
Zusätzlich zum geringen Gehalt an organischen Verbindungen in dem erfindungsgemässen Reiniger wird die Umweltbelastung durch eine wesentlich geringere Dosierung in der Spülmaschine reduziert. Die Einsatzmenge kann je nach Verschmutzungsgrad, Wasserqualität und Zustand der Spülmaschine bis zu 50 % gegenüber herkömmlichen Reinigern gesenkt werden.In addition to the low content of organic compounds in the cleaner according to the invention, the environmental impact is reduced by a much lower dosage in the dishwasher. Depending on the degree of soiling, water quality and condition of the dishwasher, the amount used can be reduced by up to 50% compared to conventional cleaners.
Als besonders vorteilhaft ist bei dem erfindungsgemässen Geschirrspülmittel festzustellen, dass bei sehr guter Reinigungsleistung über alle Anschmutzungen nach DIN 44990 und gleichzeitiger Verhinderung von Ablagerungen auf Maschinenteilen und Geschirr der Einsatz an organischen Bestandteilen für die Spülmaschine erheblich reduziert wird. Da die vorliegende Zusammensetzung auch kein Phosphat enthält und mit sehr geringer Dosierung - bis zu 50 % weniger als herkömmliche Reiniger - vergleichbare Ergebnisse zeigt, wird eine spürbare Umweltentlastung erreicht.It is particularly advantageous to determine in the dishwashing detergent according to the invention that the use of organic components for the dishwasher is considerably reduced with very good cleaning performance over all soiling in accordance with DIN 44990 and at the same time preventing deposits on machine parts and dishes. Since the present composition also contains no phosphate and, with very low doses - up to 50% less than conventional cleaners - shows comparable results, a noticeable environmental relief is achieved.
Claims (12)
gekennzeichnet durch
eine Kombination aus:
marked by
a combination of:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4114956 | 1991-05-02 | ||
| DE4114956A DE4114956A1 (en) | 1991-05-02 | 1991-05-02 | GRANULAR PHOSPHATE-FREE AGENT FOR MACHINE DISHWASHER |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0512371A2 true EP0512371A2 (en) | 1992-11-11 |
| EP0512371A3 EP0512371A3 (en) | 1995-06-14 |
| EP0512371B1 EP0512371B1 (en) | 1997-10-01 |
Family
ID=6431199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92107235A Expired - Lifetime EP0512371B1 (en) | 1991-05-02 | 1992-04-28 | Granular phosphate-free agents for automatic dishwashing |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0512371B1 (en) |
| AT (1) | ATE158812T1 (en) |
| DE (2) | DE4114956A1 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995012654A1 (en) * | 1993-11-03 | 1995-05-11 | The Procter & Gamble Company | Control of calcium carbonate precipitation in automatic dishwashing |
| EP0659874A1 (en) * | 1993-12-23 | 1995-06-28 | The Procter & Gamble Company | Detergent compositions |
| WO1995020030A1 (en) * | 1994-01-25 | 1995-07-27 | Unilever N.V. | Co-granules and detergent tablets formed therefrom |
| WO1996008552A1 (en) * | 1994-09-13 | 1996-03-21 | Kao Corporation | Washing method and clothes detergent composition |
| FR2726002A1 (en) * | 1994-10-21 | 1996-04-26 | Rhone Poulenc Chimie | COMPOSITION OF BUILDER WITHOUT ZEOLITHES OR PHOSTATES INCLUDING A SYSTEM REDUCING CALCIUM INCRUSTATIONS, ITS USE IN DETERGENT COMPOSITIONS AND THESE DETERGENT COMPOSITIONS |
| EP0812241A1 (en) * | 1995-03-01 | 1997-12-17 | Charvid Limited Liability Company | Noncaustic cleaning composition comprising peroxygen compound and specific silicate and methods of making and using same |
| EP0815192A1 (en) * | 1995-03-11 | 1998-01-07 | The Procter & Gamble Company | Detergent composition comprising a polymeric polycarboxylic compound, a chelant, and an amylase enzyme |
| US6034048A (en) * | 1995-03-01 | 2000-03-07 | Charvid Limited Liability Co. | Non-caustic cleaning composition using an alkali salt |
| WO2003038028A3 (en) * | 2001-10-30 | 2003-10-23 | Henkel Kgaa | Detergent or cleanser that can be dispersed in an essentially sediment-free manner |
| WO2006131503A2 (en) * | 2005-06-10 | 2006-12-14 | Novozymes A/S | Detergents with enzymatic builder and bleach systems |
| WO2007141635A2 (en) * | 2006-06-07 | 2007-12-13 | Silvia Palladini | Detergents formulations with low impact on the environment |
| JP2016538412A (en) * | 2013-11-11 | 2016-12-08 | エコラボ ユーエスエー インコーポレイティド | Highly alkaline article cleaning detergent with enhanced scale control and soil dispersibility |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK1307547T3 (en) | 2000-07-28 | 2006-03-20 | Henkel Kgaa | Hitherto unknown amylolytic enzyme from Bacillus sp. A 7-7 (DSM 12368) and detergents with this novel amylolytic enzyme |
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| DE3744592A1 (en) * | 1987-12-31 | 1989-07-13 | Basf Ag | Dishwashing compositions containing water-soluble polymers |
| JPH01198699A (en) * | 1988-02-03 | 1989-08-10 | Kao Corp | Detergent for automatic tableware washer |
| JPH03234795A (en) * | 1990-02-08 | 1991-10-18 | Kao Corp | Bleach composition |
| EP0504091A1 (en) * | 1991-03-15 | 1992-09-16 | Cleantabs A/S | A phosphate-free automatic dishwashing composition |
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| DE2101508C3 (en) * | 1971-01-14 | 1979-05-17 | Henkel Kgaa, 4000 Duesseldorf | Dishwashing liquid |
| DE3139091C2 (en) * | 1980-10-11 | 1986-06-19 | Sandoz-Patent-GmbH, 7850 Lörrach | Phosphate-free or low-phosphate detergents and cleaning agents |
| CA1334389C (en) * | 1986-03-26 | 1995-02-14 | Ernest H. Brumbaugh | Machine dishwasher water spot control composition |
-
1991
- 1991-05-02 DE DE4114956A patent/DE4114956A1/en not_active Ceased
-
1992
- 1992-04-28 DE DE59208935T patent/DE59208935D1/en not_active Expired - Fee Related
- 1992-04-28 AT AT92107235T patent/ATE158812T1/en not_active IP Right Cessation
- 1992-04-28 EP EP92107235A patent/EP0512371B1/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3744592A1 (en) * | 1987-12-31 | 1989-07-13 | Basf Ag | Dishwashing compositions containing water-soluble polymers |
| JPH01198699A (en) * | 1988-02-03 | 1989-08-10 | Kao Corp | Detergent for automatic tableware washer |
| JPH03234795A (en) * | 1990-02-08 | 1991-10-18 | Kao Corp | Bleach composition |
| EP0504091A1 (en) * | 1991-03-15 | 1992-09-16 | Cleantabs A/S | A phosphate-free automatic dishwashing composition |
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| Title |
|---|
| DATABASE WPI Week 8938, Derwent Publications Ltd., London, GB; AN 89-274105 & JP-A-1 198 699 (KAO) 10. August 1989 * |
| DATABASE WPI Week 9148, Derwent Publications Ltd., London, GB; AN 91-350051 & JP-A-3 234 795 (KAO) 18. Oktober 1991 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995012654A1 (en) * | 1993-11-03 | 1995-05-11 | The Procter & Gamble Company | Control of calcium carbonate precipitation in automatic dishwashing |
| EP0659874A1 (en) * | 1993-12-23 | 1995-06-28 | The Procter & Gamble Company | Detergent compositions |
| AU702040B2 (en) * | 1994-01-25 | 1999-02-11 | Unilever Plc | Co-granules and detergent tablets formed therefrom |
| WO1995020030A1 (en) * | 1994-01-25 | 1995-07-27 | Unilever N.V. | Co-granules and detergent tablets formed therefrom |
| WO1996008552A1 (en) * | 1994-09-13 | 1996-03-21 | Kao Corporation | Washing method and clothes detergent composition |
| CN1093169C (en) * | 1994-09-13 | 2002-10-23 | 花王株式会社 | Washing method and clothes detergent composition |
| FR2726002A1 (en) * | 1994-10-21 | 1996-04-26 | Rhone Poulenc Chimie | COMPOSITION OF BUILDER WITHOUT ZEOLITHES OR PHOSTATES INCLUDING A SYSTEM REDUCING CALCIUM INCRUSTATIONS, ITS USE IN DETERGENT COMPOSITIONS AND THESE DETERGENT COMPOSITIONS |
| WO1996012784A1 (en) * | 1994-10-21 | 1996-05-02 | Rhone-Poulenc Chimie | Zeolite and phosphate-free detergent builder composition |
| US6043207A (en) * | 1995-03-01 | 2000-03-28 | Charvid Limited Liability Co. | Non-caustic cleaning composition comprising peroxygen compound, meta/sesqui-silicate, chelate and method of making same in free-flowing, particulate form |
| EP0812241A4 (en) * | 1995-03-01 | 1999-08-18 | Charvid Limited Liability Comp | Noncaustic cleaning composition comprising peroxygen compound and specific silicate and methods of making and using same |
| US6034048A (en) * | 1995-03-01 | 2000-03-07 | Charvid Limited Liability Co. | Non-caustic cleaning composition using an alkali salt |
| EP0812241A1 (en) * | 1995-03-01 | 1997-12-17 | Charvid Limited Liability Company | Noncaustic cleaning composition comprising peroxygen compound and specific silicate and methods of making and using same |
| EP0815192A4 (en) * | 1995-03-11 | 1999-09-22 | Procter & Gamble | Detergent composition comprising a polymeric polycarboxylic compound, a chelant, and an amylase enzyme |
| EP0815192A1 (en) * | 1995-03-11 | 1998-01-07 | The Procter & Gamble Company | Detergent composition comprising a polymeric polycarboxylic compound, a chelant, and an amylase enzyme |
| WO2003038028A3 (en) * | 2001-10-30 | 2003-10-23 | Henkel Kgaa | Detergent or cleanser that can be dispersed in an essentially sediment-free manner |
| WO2006131503A2 (en) * | 2005-06-10 | 2006-12-14 | Novozymes A/S | Detergents with enzymatic builder and bleach systems |
| WO2006131503A3 (en) * | 2005-06-10 | 2007-09-07 | Novozymes As | Detergents with enzymatic builder and bleach systems |
| WO2007141635A2 (en) * | 2006-06-07 | 2007-12-13 | Silvia Palladini | Detergents formulations with low impact on the environment |
| WO2007141635A3 (en) * | 2006-06-07 | 2008-09-04 | Silvia Palladini | Detergents formulations with low impact on the environment |
| JP2016538412A (en) * | 2013-11-11 | 2016-12-08 | エコラボ ユーエスエー インコーポレイティド | Highly alkaline article cleaning detergent with enhanced scale control and soil dispersibility |
| EP3068857A4 (en) * | 2013-11-11 | 2017-07-12 | Ecolab USA Inc. | High alkaline warewash detergent with enhanced scale control and soil dispersion |
| JP2018159082A (en) * | 2013-11-11 | 2018-10-11 | エコラボ ユーエスエー インコーポレイティド | High alkaline warewash detergent with enhanced scale control and soil dispersion |
| US10316272B2 (en) | 2013-11-11 | 2019-06-11 | Ecolab Usa Inc. | High alkaline warewash detergent with enhanced scale control and soil dispersion |
| US10745651B2 (en) | 2013-11-11 | 2020-08-18 | Ecolab Usa Inc. | High alkaline warewash detergent with enhanced scale control and soil dispersion |
| US11339354B2 (en) | 2013-11-11 | 2022-05-24 | Ecolab Usa Inc. | High alkaline warewash detergent with enhanced scale control and soil dispersion |
| US11920109B2 (en) | 2013-11-11 | 2024-03-05 | Ecolab Usa Inc. | High alkaline warewash detergent with enhanced scale control and soil dispersion |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4114956A1 (en) | 1992-11-05 |
| DE59208935D1 (en) | 1997-11-06 |
| EP0512371B1 (en) | 1997-10-01 |
| ATE158812T1 (en) | 1997-10-15 |
| EP0512371A3 (en) | 1995-06-14 |
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